CN107075425B - Additive for reducing stains in automatic dishwashing systems - Google Patents

Additive for reducing stains in automatic dishwashing systems Download PDF

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Publication number
CN107075425B
CN107075425B CN201580052156.7A CN201580052156A CN107075425B CN 107075425 B CN107075425 B CN 107075425B CN 201580052156 A CN201580052156 A CN 201580052156A CN 107075425 B CN107075425 B CN 107075425B
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acid
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acrylamido
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CN107075425A (en
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S·巴克尔
S·费里尤克斯
P·梅尔坎多
E·P·沃瑟曼
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Rohm and Haas Co
Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/391—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A phosphorus-free automatic dishwashing detergent composition comprising: (a)0.5 to 8 wt% of a first polymer comprising polymerized units of: (i)60 to 82 wt% (meth) acrylic acid, (ii)10 to 30 wt% monoethylenically unsaturated dicarboxylic acid, and (iii)8 to 25 wt% 2-acrylamido-2-methylpropanesulfonic Acid (AMPS); and has M of 5,000 to 100,000w(ii) a (b)0.5 to 8 wt% of a second polymer comprising polymerized units of: (i)60 to 95 wt% (meth) acrylic acid, (ii)5 to 40 wt% 2-acrylamido-2-methylpropanesulfonic Acid (AMPS); and has M of 5,000 to 100,000w(ii) a (c)15 to 50 wt% carbonate, (d)5 to 50 wt% citrate, and (e)10 to 30 wt% bleach.

Description

Additive for reducing stains in automatic dishwashing systems
Background
The present invention relates generally to detergent compositions for reducing stains in non-phosphate automatic dishwashing systems.
Automatic dishwashing detergents are known as a class of detergent compositions different from those used for fabric washing or water treatment. Automatic dishwashing detergents are needed to produce a stain-free and film-free appearance on washed items after a thorough cleaning cycle. Phosphate-free compositions rely on non-phosphate builders, such as citrates, carbonates, silicates, disilicates, bicarbonates, aminocarboxylates, and others, to sequester calcium and magnesium from hard water and leave insoluble visible deposits after drying. Polymers prepared from acrylic acid, maleic acid, and 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) are known to inhibit the fouling produced by non-phosphate builders. For example, U.S. publication No. 2010/0234264 discloses a polymer prepared from acrylic acid, maleic acid, and AMPS in a detergent composition. However, this reference does not disclose the compositions of the present invention, which provide improved performance.
Disclosure of Invention
The present invention relates to a phosphorus-free automatic dishwashing detergent composition comprising: (a)0.5 to 8 wt% of a first polymer comprising polymerized units of: (i)60 to 82 wt% (meth) acrylic acid, (ii)10 to 30 wt% monoethylenically unsaturated dicarboxylic acid, and (iii)8 to 25 wt% 2-acrylamido-2-methylpropanesulfonic Acid (AMPS); and has M of 5,000 to 100,000w(ii) a (b)0.5 to 8 wt% of a second polymer comprising polymerized units of: (i)60 to 95 wt% (meth) acrylic acid, (ii)5 to 40 wt% 2-acrylamido-2-methylpropanesulfonic Acid (AMPS); and has M of 5,000 to 100,000w(ii) a (c)15 to 50 wt% carbonate, (d)5 to 50 wt% citrate, and (e)10 to 30 wt% bleach.
Detailed Description
Unless otherwise indicated, all percentages are weight percentages (wt%) and all temperaturesAll in degrees Celsius. The weight average molecular weight M is measured by Gel Permeation Chromatography (GPC) using polyacrylic acid standards, as known in the artw. The technique of GPC is discussed in detail in the following documents: modern Size Exclusion Chromatography (Modern Size Exclusion Chromatography), w.w.yau, j.j.kirkland, d.d.bly; welfare interdiscipline (Wiley Interscience), 1979, and Guide for materials Characterization and Chemical Analysis (a Guide materials Characterization and Chemical Analysis), j.p. siiibia; VCH, 1988, pages 81-84. Molecular weights reported herein are in daltons. As used herein, the term "(meth) acrylic" refers to acrylic or methacrylic; the term "carbonate" refers to an alkali metal or ammonium salt of carbonate, bicarbonate, percarbonate, sesquicarbonate; the term "silicate" refers to an alkali metal or ammonium salt of silicate, disilicate, metasilicate; and the term "citrate" refers to citrate. Preferably, the carbonate, silicate or citrate is a sodium, potassium or lithium salt; preferably sodium or potassium; sodium salts are preferred. The weight percentage of carbonate or citrate is based on the actual weight of the salt including the metal ion. The term "phosphorus-free" refers to compositions, preferably undetectable phosphorus, containing less than 0.5 wt%, preferably less than 0.2 wt%, preferably less than 0.1 wt% phosphorus (as elemental phosphorus). The weight percentage in the detergent composition is a percentage of the dry weight, i.e. excluding any water monomer units that may be present in the detergent composition as a percentage of the weight of solids in the polymer, i.e. excluding any water present in the polymer emulsion.
Preferably, the amount of citrate in the detergent composition is at least 8 wt%, preferably at least 10 wt%, preferably at least 15 wt%, preferably at least 20 wt%, preferably at least 25 wt%; preferably not more than 45 wt%, preferably not more than 40 wt%, preferably not more than 35 wt%. Preferably, the amount of carbonate is at least 20 wt%, preferably at least 22 wt%, preferably not more than 45 wt%, preferably not more than 40 wt%, preferably not more than 35 wt%, preferably not more than 30 wt%. Preferably, the bleaching agent is percarbonate or perborate. Preferably, the amount of bleaching agent is at least 11 wt%, preferably at least 12 wt%, preferably at least 13 wt%; preferably not more than 25 wt%, preferably not more than 22 wt%, preferably not more than 20 wt%, preferably not more than 18 wt%.
Preferably, the detergent composition comprises an aminocarboxylate builder, preferably in an amount of from 1 wt% to 35 wt%; preferably at least 1.5 wt%, preferably at least 2 wt%, preferably at least 5 wt%; preferably at least 10 wt%; preferably not more than 30 wt%, preferably not more than 25 wt%, preferably not more than 20 wt%. A preferred aminocarboxylate builder is methylglycine diacetic acid (MGDA).
Preferably, the first polymer and the second polymer are present in a weight ratio (first: second) of 1:9 to 9:1, respectively; preferably 1:6 to 6:1, preferably 1:4 to 4:1, preferably 1:3 to 4:1, preferably 1:2 to 3.5: 1. Preferably, the total amount of the first polymer and the second polymer in the composition is from 1.5 wt% to 12 wt%, preferably from 2 wt% to 11 wt%, preferably from 2 wt% to 10 wt%, preferably from 2.5 wt% to 9 wt%. Preferably, the composition comprises at least 1 wt% of the first polymer, preferably at least 1.5 wt%, preferably at least 2 wt%, preferably at least 2.5 wt%; preferably at least 3 wt%, preferably not more than 7.5 wt%, preferably not more than 7 wt%, preferably not more than 6.5 wt%. Preferably, the composition comprises at least 0.7 wt% of the second polymer, preferably at least 0.9 wt%, preferably at least 1.2 wt%, preferably at least 1.5 wt%, preferably at least 1.8 wt%; preferably not more than 7 wt%, preferably not more than 6.5 wt%, preferably not more than 6 wt%.
Preferably, the first polymer comprises at least 63 wt% polymerized units of (meth) acrylic acid, preferably at least 65 wt%, preferably at least 67 wt%, preferably at least 68 wt%; preferably not more than 78 wt%, preferably not more than 76 wt%, preferably not more than 74 wt%. Preferably, the monoethylenically unsaturated dicarboxylic acid units are at least 12 wt.% of the first polymer, preferably at least 14 wt.%, preferably at least 16 wt.%, preferably at least 18 wt.%; preferably not more than 28 wt%, preferably not more than 26 wt%, preferably not more than 24 wt%.
For both the first polymer and the second polymer, where the monoethylenically unsaturated dicarboxylic acid may be in the form of an anhydride, the polymer is prepared via polymerization of the anhydride, which is hydrolyzed to the acid during the polymerization process, resulting in polymerized units of the monoethylenically unsaturated dicarboxylic acid. All references to polymeric dicarboxylic acid units in the polymer include metal salts of the acids, which will be present at pH values near or above the pKa of the carboxylic acid groups. Preferably, the monoethylenically unsaturated dicarboxylic acid has from 4 to 6 carbon atoms, preferably 4 or 5 carbon atoms. Preferably, the monoethylenically unsaturated dicarboxylic acid is selected from the group consisting of: maleic acid, fumaric acid, itaconic acid, mesaconic acid, and citraconic acid; preferably maleic acid.
Preferably, the amount of polymerized AMPS units (including metal or ammonium salts) in the first polymer is at least 8.5 wt%, preferably at least 9 wt%; preferably not more than 20 wt%, preferably not more than 17 wt%, preferably not more than 15 wt%, preferably not more than 13 wt%. Preferably, the total amount of monoethylenically unsaturated dicarboxylic acid and AMPS units in the first polymer is at least 24 weight percent, preferably at least 26 weight percent, preferably at least 28 weight percent, preferably at least 29 weight percent, preferably at least 30 weight percent.
Preferably, the second polymer comprises polymerized units of at least 65 wt% (meth) acrylic acid, preferably at least 70 wt%, preferably at least 75 wt%, preferably at least 80 wt%, preferably at least 85 wt%; preferably not more than 94 wt%, preferably not more than 93 wt%, preferably not more than 92 wt%. Preferably, the amount of AMPS residue (including metal or ammonium salts) in the second polymer is at least 6 wt%, preferably at least 7 wt%, preferably at least 8 wt%; preferably not more than 35 wt%, preferably not more than 30 wt%, preferably not more than 25 wt%, preferably not more than 20 wt%, preferably not more than 15 wt%.
Preferably, the polymer contains no more than 8 wt% polymerized units of acrylate or methacrylate, preferably no more than 5 wt%, preferably no more than 3 wt%, preferably no more than 1 wt%.
Preferably, the polymer has an M of at least 8,000wPreferably at least 9,000, preferably at least 10,000, preferably at least 11,000, preferably at least 12,000; preferably not more than 70,000, preferably not more than 50,000, preferably not more than 30,000, preferably not more than 25,000.
The polymer may be used in combination with other polymers useful for controlling insoluble deposits in automatic dishwashing machines, including, for example, polymers comprising a combination of residues of: acrylic acid monomers, methacrylic acid monomers, residues of maleic acid monomers or other diacid monomers, esters of acrylic acid or methacrylic acid (including polyethylene glycol esters), styrene monomers, AMPS and other sulfonated monomers, and substituted acrylamides or methacrylamides.
The polymers of the present invention may be produced by any known technique for polymerizing acrylic monomers. Preferably, the initiator is free of phosphorous. Preferably, the polymer contains less than 1 wt% phosphorus, preferably less than 0.5 wt%, preferably less than 0.1 wt%, preferably the polymer is phosphorus free. Preferably, the polymerization is initiated using a persulfate salt and the end group on the polymer is a sulfate or sulfonate. The polymer may take the form of an aqueous solution polymer, a slurry, a dry powder or granules or other solid form.
Other components of automatic dishwashing detergent compositions may include, for example, surfactants, oxygen and/or chlorine bleaches, bleach activators, enzymes, suds suppressors, pigments, perfumes, antibacterial agents and fillers. Typical surfactant levels depend on the specific surfactant(s) used; preferably the total amount of surfactant is from 0.5 wt% to 15 wt%, preferably at least 0.7 wt%, preferably at least 0.9 wt%; preferably not more than 10 wt%, preferably not more than 7 wt%, preferably not more than 4 wt%, preferably not more than 2 wt%, preferably not more than 1 wt%. Preferably, the surfactant comprises a nonionic surfactant. Preferably, the nonionic surfactant has the formula RO- (M)x(N)y-OH or R-O- (M)x(N)y-O-R', wherein M and N are units derived from an alkylene oxide, one of which is ethylene oxide, and R represents C6-C22Straight or branched chain alkyl, and R' represents a group derived from an ethanol precursor and C6-C22Linear or branched alkyl halides, alkylene oxides or glycidyl ethers. With fillers in the form of tablets or powders as inert water-soluble substances, usually sodium or potassium salts, e.g. sodium or potassium sulfate andor sodium chloride or potassium chloride, and is typically present in an amount in the range of from 0 wt% to 75 wt%. Fillers in gel formulations may include those mentioned above as well as water. Fragrances, dyes, suds suppressors, enzymes and antibacterial agents generally collectively are no more than 5% by weight of the composition.
Preferably, the composition has a pH of at least 10 (at 1 wt% in water), preferably at least 11.5; in some embodiments, the pH is no greater than 13.
The compositions may be formulated in any typical form, for example, as tablets, powders, unit doses, sachets, pastes, liquids or gels. The composition may be used in any typical automatic dishwashing machine under typical operating conditions. Typical water temperatures during the washing process are preferably from 20 ℃ to 85 ℃, preferably from 30 ℃ to 70 ℃. Typical concentrations of the composition, such as the percentage of total liquid in the dish washing machine, are preferably 0.1 wt% to 1 wt%, preferably 0.2 wt% to 0.7 wt%. With the selection of the appropriate product form and addition time, the composition may be present in a pre-wash, a main wash, a penultimate rinse, a last rinse, or any combination of these cycles.
Examples of the invention
Synthesis of example terpolymers
Phosphate-free ADW
The target is as follows: preparation of AA/maleic acid/AMPS// 70 wt%/20 wt%/10 wt%
Dispersant, Mw-15K
Figure BDA0001255254080000041
Figure BDA0001255254080000051
Figure BDA0001255254080000052
And (3) characterization:
Figure BDA0001255254080000053
other polymers were prepared using the same method.
Other polymers were prepared using the same method.
Preparation of food dirt:
Figure BDA0001255254080000061
1. bringing the water to boiling.
2. Mix in 16 oz paper cup: instant gravy, benzoic acid and starch; the mixture was added to boiling water.
3. Adding milk and margarine.
4. The mixture was cooled to about 40 ℃.
5. The mixture was filled into the tank of a kitchen machine (Baoqiao).
6. The egg yolk, ketchup and mustard were mixed in a 16 ounce paper cup using a spoon.
7. The cooled mixture was added to the tank with continuous stirring.
8. The mixture was stirred for 5 minutes.
9. The mixture was frozen.
10. Before starting the protocol, the frozen soil was placed into the dish washing machine.
Dishwashing test conditions:
Figure BDA0001255254080000062
Figure BDA0001255254080000071
the food soil was loaded when the detergent was loaded into the wash liquor (20min mark).
After drying in open air, both glasses were rated from 1 (clean) to 5 (severe fouling) for both fouling and staining by two trained observers. (see ASTM-D3556-85.)
Abbreviations:
AA acrylic acid
ADW automatic tableware washing machine
AMPS 2-acrylamido-2-methyl-1-propanesulfonic acid
EA Ethyl acrylate
IA itaconic acid
Mal maleic acid
MGDA methylglycine diacetic acid sodium salt
Mn number average molecular weight
Mw weight average molecular weight
TAED tetraacetylethylenediamine
TABLE 1 polymers for automatic dishwashing examples
Figure BDA0001255254080000072
Monomer mixture for polymer G further contained 10% ethyl acrylate
Table 2 ADW example 1: performance in citrate-based formulations
Figure BDA0001255254080000073
Figure BDA0001255254080000081
aBritesil H20, PQ corporation;btrilon M, basf.
Table 3 ADW example 2: polymer composition change, mol.
Figure BDA0001255254080000082
Figure BDA0001255254080000091
aBritesil H20, PQ corporation;btrilon M, BassProvided is a method for producing a novel compound.
Table 4 ADW example 3: performance in Mixed citrate/MGDA formulations
Figure BDA0001255254080000092
aBritesil H20, PQ corporation;btrilon M, basf.
Table 5 ADW example 4: performance in MGDA-based formulations
Figure BDA0001255254080000093
Figure BDA0001255254080000101
aBritesil H20, PQ corporation;btrilon M, basf.
Table 6 ADW example 5: properties in surfactant-free formulations
Figure BDA0001255254080000102
Figure BDA0001255254080000111
aBritesil H20, PQ corporation;btrilon M, basf.
Table 7 ADW example 6: effect on citrate-based formulations as disilicate content varied
Figure BDA0001255254080000112
aBritesil H20, PQ corporation;btrilon M, basf.
Table 8 ADW example 7: performance in high carbonate matrices
Figure BDA0001255254080000121
aBritesil H20, PQ corporation;btrilon M, basf.

Claims (7)

1. A phosphorus-free automatic dishwashing detergent composition comprising:
(a)1.5 to 8 wt% of a first polymer comprising polymerized units of: (i)65 to 76 wt% (meth) acrylic acid, (ii)16 to 26 wt% monoethylenically unsaturated dicarboxylic acid, wherein the monoethylenically unsaturated dicarboxylic acid is selected from the group consisting of: (ii) maleic, fumaric, itaconic, mesaconic and citraconic acids, and (iii)8 to 17 weight percent 2-acrylamido-2-methylpropanesulfonic acid; and has M of 5,000 to 100,000w；
(b)0.5 to 8 wt% of a second polymer comprising polymerized units of: (i)60 to 95 wt% (meth) acrylic acid, (ii)5 to 40 wt% 2-acrylamido-2-methylpropanesulfonic Acid (AMPS);
and has M of 5,000 to 100,000w；
(c)15 to 50 wt% of a carbonate salt,
(d) from 5 wt% to 50 wt% citrate, and
(e)10 to 30% by weight of a bleaching agent,
wherein the composition comprises a total of from 2 wt% to 10 wt% of the first polymer and the second polymer,
wherein the weight ratio of the first polymer to the second polymer is 1:2 to 3.5: 1.
2. the composition of claim 1, wherein the composition comprises 20 wt% to 45 wt% carbonate.
3. The composition of claim 1, wherein the composition contains less than 0.2 wt% phosphorus.
4. The composition of claim 3, wherein the first polymer comprises polymerized units of: (i)65 to 75% by weight of acrylic acid, (ii)16 to 26% by weight of monoethylenically unsaturated dicarboxylic acid, and (iii)8 to 17% by weight of 2-acrylamido-2-methylpropanesulfonic acid.
5. The composition of claim 4, wherein the second polymer comprises polymerized units of: (i)75 to 93 wt% acrylic acid, and (ii)7 to 25 wt% 2-acrylamido-2-methylpropanesulfonic acid.
6. The composition of claim 5, wherein the first polymer and the second polymer each have an M of 8,000 to 50,000w。
7. The composition of claim 6, wherein the composition comprises 20 wt% to 40 wt% citrate.
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US10781399B2 (en) 2016-12-16 2020-09-22 Dow Global Technologies Llc Additive for controlling spotting in automatic dishwashing systems
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